EP1109860B1 - Matiere moulable asa pour la production de pieces de moulage mates - Google Patents

Matiere moulable asa pour la production de pieces de moulage mates Download PDF

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Publication number
EP1109860B1
EP1109860B1 EP99944455A EP99944455A EP1109860B1 EP 1109860 B1 EP1109860 B1 EP 1109860B1 EP 99944455 A EP99944455 A EP 99944455A EP 99944455 A EP99944455 A EP 99944455A EP 1109860 B1 EP1109860 B1 EP 1109860B1
Authority
EP
European Patent Office
Prior art keywords
weight
particularly preferably
molding composition
gew
bis
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Revoked
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EP99944455A
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German (de)
English (en)
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EP1109860A1 (fr
Inventor
Heiner GÖRRISSEN
Herbert Morgenstern
Graham Edmund Mc Kee
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BASF SE
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BASF SE
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
    • B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07—Flat, e.g. panels
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C51/00—Shaping by thermoforming, i.e. shaping sheets or sheet like preforms after heating, e.g. shaping sheets in matched moulds or by deep-drawing; Apparatus therefor
    • B29C51/08—Deep drawing or matched-mould forming, i.e. using mechanical means only

Definitions

  • the invention relates to thermoplastic molding compositions made from a polystyrene-acrylonitrile polymer and a multi-phase cross-linked rubber produced molding materials and processes for the production of molding materials by Coextrusion.
  • thermoplastic polymer materials especially in the automotive interior, household, electrical and Sports equipment is increasingly becoming a glare-free, matt surface desired, for which decorative reasons or also security aspects, e.g. reduced Glare to the driver and improved performance characteristics-fingerprints are barely visible on matt surfaces - they should be mentioned.
  • security aspects e.g. reduced Glare to the driver and improved performance characteristics-fingerprints are barely visible on matt surfaces - they should be mentioned.
  • most commercially impact-modified molding compositions deliver Shaped bodies with a glossy surface.
  • Matte molded parts can be made by treating the surface of the finished, Achieve normal gloss molded part, for example by mechanical Roughening like grinding and brushing, through etching, dissolving and swelling or by applying a matt coating layer. Common to all processes is the disadvantage of an additional step on the finished molded part.
  • pressing and molding tools with a structured surface can also be used to produce molded parts with a matt surface, but the structure of the tool wears out relatively quickly.
  • inorganic matting agents such as silica gel or chalk to polymers has the disadvantage that the mechanical properties of the moldings are impaired.
  • organic Avoid matting agents consist of comparatively large particles Diameter (D> about 0.5 microns) which are dispersed in matrix polymers. The Particles emerge somewhat from the smooth and thus shiny surface of the Matrix polymer and in this way cause a diffuse reflection of the occurring light (scattering), which makes the surface matt for the viewer appears.
  • matt and impact-resistant polymers are required. If a hard, brittle polymer is to be modified in one step, the large, matting particles must also be rubber-elastic Have properties. To the matting rubber particles with the compatible or at least partially compatible with non-elastic matrix polymers make, the former are mostly compatible with a graft cover from such or partially compatible polymers.
  • EP-A 576 960 there is another way of achieving matt, impact-resistant Molding compounds in it, larger particles by agglomeration of small particles to produce such graft polymers that are acidic in the graft core and in the shell contain basic groups or vice versa. The one to be achieved in this way In some cases, the matting effect is limited.
  • thermoplastic molding compositions with improved To provide surface properties that are both matt and free of Are flow lines.
  • thermoplastic molding compositions according to the invention are characterized in that that the polymer A has a viscosity number, measured as a 0.5% solution in Dimethylformamide at 23 ° C, from 50 to 70 ml / g, preferably from 55 to 65 ml / g, and that at least 80% by number, preferably at least 85% by number, particularly preferably at least 90% by number of the rubber particles B in the Dispersion after its production a diameter of ⁇ 0.2 microns, preferably ⁇ 0.18 ⁇ m, particularly preferably ⁇ 0.15 ⁇ m.
  • This product class has the name ASA because it consists of acrylonitrite, styrene and an acrylate. It has surprisingly been found that when molding compounds made of a polystyrene-acrylonitrile matrix and crosslinked rubber particles embedded therein, a rough surface that scatters the light and thus gives a matt appearance, with rubber particles of small diameter dispersed in the polystyrene-acrylonitrile matrix is achieved and that the surface of the molding materials obtained after coextrusion with other plastics, in particular ABS, is free from flow lines if a smooth-flowing polystyrene-acrylonitrile matrix is used.
  • Preferred as further monomers a3) are (meth) acrylic acid and / or their Derivatives, especially methyl methacrylate, acrylamide and / or methacrylamide as well as maleic anhydride and / or phenylmaleimide.
  • Phase b1) of the crosslinked rubber B which preferably has a glass transition temperature of ⁇ 0 ° C, preferably ⁇ -10 ° C, particularly preferably ⁇ -15 ° C, has, is predominantly made of acrylates (80 to 100 wt .-%, preferably 90 to 100% by weight, particularly preferably 95 to 100% by weight) of acrylates, in particular Butyl acrylate and / or ethylhexyl acrylate.
  • This rubber phase b1) can further monomers b1.2), in particular methacrylates, styrene and / or acrylonitrile contain.
  • Particularly preferred monomers b1.2) are polyfunctional crosslinking Monomers which are preferably selected from the following group: divinylbenzene, Diallyl maleate, diallyl fumarate, diallyl phthalate, allyl methacrylate, triallyl isocyanurate, Butadiene, isoprene, dihydrodicyclopentadienyl acrylate, especially preferably dihydrodicyclopentadienyl acrylate.
  • the rubber phase b1) is by emulsion polymerization of the monomers or produced by mini-emulsion polymerization.
  • the same substances are suitable as further monomers b2.3) as for other b1.2) Monomers listed for the first phase.
  • the second phase b2) is usually the outer phase of rubber B, i.e. the rubber B is usually as Core / shell polymer before, but this structure is not mandatory.
  • the rubber phase b2) is preferably compatible or partially compatible with the Matrix component A of the thermoplastic molding compositions.
  • the rubber B can have further polymer phases, in particular of polystyrene and its copolymers, preferably of polystyrene and crosslinking agents and / or graft-active monomers. These phases can be formed on outer shells or can also form the cores of the multiphase rubber particles B.
  • the viscosity number of polymer A is measured in accordance with DIN 53726 on a 0.5% strength solution of the polymer in dimethylformamide at 23 °.
  • the diameter of the rubber particles B and their number were determined using the analytical ultracentrifuge in accordance with the method of W. Scholtan and H. Lange, Kolloid-Z. and Z.-Polymer 250 (1972) pages 782 to 796.
  • the ultracentrifuge measurement provides the integral mass distribution or number distribution of the particle diameter of a sample. From this it can be deduced what number or weight percent of the particles have a diameter equal to or smaller than a certain size.
  • the rubber B has a third phase, this preferably consists of at least one 80% by weight of styrene and / or its derivatives. It preferably forms the core or one Intermediate shell of the polymer particles.
  • thermoplastic molding compositions preferably have a melt index of at least 2 ml / 10 min, preferably at least 4 ml / 10 min.
  • the melt index was determined according to ISO 1133 at 220 ° C and 10 kg.
  • the invention further relates to molding materials, in particular profiles, foils or Sheets produced by coextrusion of 0.1 to 50% by weight, preferably 2 to 20 Wt .-% molding compositions according to any one of claims 1 to 3, and 50 to 99.9 wt .-%, preferably 80 to 98% by weight of a second thermoplastic molding composition from one of the following polymers: ABS, PVC, HIPS, SAN, ASA + PC or ABS + PC.
  • the processing products of molding compositions are referred to as molding materials in a known manner.
  • the ratio of the melt indices of the first to the second molding composition, according to ISO 1133 at 220 ° C. and 10 kg, is preferably in the range from 0.5 to 10, particularly preferably in the range from 1 to 10.
  • the acrylonitrile content of the first molding compound is preferably greater than that Acrylonitrile content of the second molding compound.
  • Molded materials whose rubber particles B have a network morphology are particularly suitable have, i.e. that at least 80 number% of the particles each have a point of contact with another particle.
  • the object of the invention is also achieved by blends from the above defined thermoplastic molding compositions with up to 45 wt .-% thermoplastic Molding compositions achieved that have the same chemical structure, however the viscosity number of the polymer A as well as the size of the rubber particles B can be arbitrary.
  • the invention also relates to a process for the production of molded materials by coextrusion, the coextruded moldings preferably being deep-drawn and, preferably, the processing temperature of the first Molding composition at 200 to 300 ° C, in particular at 210 to 280 ° C.
  • the molding compositions according to the invention are particularly suitable for the production of Window profiles, housings, clothing parts, covers, boats, roofs or Roof boxes.
  • a first thermoplastic molding compound (ASA1) of 55% by weight was used Polystyrene acrylonitrile with a viscosity number of 80 ml / g and an acrylonitrile content of 35% and 45% by weight of monodispersed butyl acrylate graft rubber with a Particle size of 0.5 ⁇ m.
  • the graft rubber was made by the emulsion polymerization process produced: In a first polymerization stage a mixture of butyl acrylate (BA) and dihydrodicyclopentadienyl acrylate (DCPA) polymerized in a weight ratio of 98: 2.
  • the rubber particles obtained in the first step became the polymerization step grafted with styrene (S) and acrylonitrile (AN).
  • the SAN: BA + weight ratio DCPA was 40:60.
  • After making the rubber dispersion had more than 99% by number of the rubber particles with a diameter> 0.2 ⁇ m.
  • the Particle size distribution of the dispersion was measured using the ultracentrifuge.
  • the graft rubber dispersion was coagulated and the centrifugal moisture Rubber with a PSAN melt at 260 ° C in a ZSK extruder from the company Werner and Pfleiderer mixed.
  • thermoplastic molding composition ASA 1 left unchanged and each with different, second, ABS molding compounds, co-extruded as listed below:
  • ABS 1 viscosity number of the matrix 80 ml / g, acrylonitrile content of the matrix 24%, Rubber content 30%, melt index at 220 ° C and 10 kg 6 ml / 10 min and weight-average diameter of 0.35 ⁇ m.
  • ABS 3 viscosity number of the matrix 80 ml / g, acrylonitrile content of the matrix 35% by weight, rubber content 28%, melt index at 220 ° and 10 kg 4.5 ml / 10 min and weight-average diameter of 0.35 ⁇ m.
  • ABS 4 viscosity number of the matrix 80 ml / g, acrylonitrile content of the matrix 33%, rubber content 46%, weight average diameter of 0.35 ⁇ m.
  • ABS 5 Cycolac® GPX 3700 from General Electric Plastics. In all of Comparative Examples 1 to 5, glossy plate surfaces were used receive.
  • the first was thermoplastic Molding compound a molding compound ASA 2 made of 55 wt .-% polystyrene acrylonitrile with a Viscosity number of 80 ml / g and an acrylonitrile content of 35% and 45% by weight Butyl acrylate graft rubber used with a particle size of 0.1 microns.
  • the SAN: BA + DCPA weight ratio was 40:60.
  • the molding compound was in manufactured in the same way as ASA 1. Had in the ASA 2 dispersion obtained more than 99% by number of particles with a diameter ⁇ 0.2 ⁇ m.
  • the molding compound ASA 2 was then with each of the second listed above Molding compositions ABS 1 to ABS 5 each co-extruded. In all examples 6 to 10 the surfaces of the coextruded sheets were matt, but showed flow lines.
  • the first molding compound (ASA 3) was a mixture of 55% by weight of polystyrene-acrylonitrile with a viscosity number of 60 ml / g and an acrylonitrile content of 35% and 45 wt .-% butyl acrylate graft rubber.
  • the butyl acrylate graft rubber was the same as for ASA 2.
  • the first molding compound was ASA 3 then one after the other with one of the molding compounds listed above ABS 1 to 5 co-extruded as a second molding compound. In all examples 11 to 15 coextruded sheets were obtained with matte lines free of flow lines Surfaces.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Claims (11)

  1. Masses de moulage thermoplastiques, contenant
    A) 20 à 90% en poids, de préférence 30 à 80% en poids, particulièrement avantageusement 40 à 75% en poids, d'un polymère thermoplastique, constitué d'unités qui dérivent
    a1) de 60 à 85% en poids, de préférence de 63 à 81% en poids, particulièrement avantageusement de 65 à 80% en poids, de styrène et/ou de styrène substitué, en particulier d'α-méthytstyrène,
    a2) de 15 à 40% en poids, de préférence de 19 à 37% en poids, particulièrement avantageusement de 20 à 35% en poids, d'acrylonitrile, et
    a3) de 0 à 25% en poids, de préférence de 0 à 20% en poids, particulièrement avantageusement de 0 à 18% en poids, d'autres monomères copolymérisables avec a1 et a2, et
    B) 10 à 80% en poids, de préférence 20 à 70% en poids, particulièrement avantageusement 25 à 60% en poids, d'un caoutchouc de greffage réticulé, polyphasique, à base
    b1) de 30 à 90% en poids, de préférence de 40 à 70% en poids, particulièrement avantageusement de 45 à 70% en poids, d'une phase préparée par polymérisation en émulsion ou en miniémulsion de
    b1.1) 80 à 100% en poids, de préférence 90 à 100% en poids, particulièrement avantageusement 95 à 100% en poids, d'un acrylate et de
    b1.2) 0 à 20% en poids, de préférence 0 à 10% en poids, particulièrement avantageusement 0 à 5% en poids, d'autres monomères, et
    b2) de 10 à 70% en poids, de préférence de 30 à 60% en poids, particulièrement avantageusement de 30 à 55% en poids, d'au moins une autre phase préparée par polymérisation de
    b2.1) 60 à 85% en poids, de préférence 70 à 80% en poids, de styrène,
    b2.2) 15 à 35% en poids, de préférence 20 à 30% en poids, d'acrylonitrile et
    b2.3) 0 à 20% en poids d'autres monomères, en présence de la première phase,
       le polymère A présentant un indice de viscosité, mesuré sous la forme d'une solution à 0,5% dans du diméthylformamide à 23°C (DIN 53726), de 50 à 70 ml/g, de préférence de 55 à 65 ml/g, et au moins 80% en nombre, de préférence au moins 85% en nombre, particulièrement avantageusement au moins 90% en nombre, des particules de caoutchouc B dans la dispersion présentant après leur préparation un diamètre de <0,2 µm, de préférence de <0,18 µm, particulièrement avantageusement de <0,15 µm (mesure à ultracentrifugation selon Scholtan et Lange).
  2. Masses de moulage thermoplastiques suivant la revendication 1, caractérisées en ce que le caoutchouc B présente une troisième phase, qui est préparée de préférence par polymérisation d'au moins 80% en poids de styrène et/ou de ses dérivés.
  3. Masses de moulage thermoplastiques suivant l'une des revendications 1 et 2, caractérisées par un indice de fusion d'au moins 2 ml/10 minutes, de préférence d'au moins 4 ml/10 minutes (selon ISO 1133 à 220°C et 10 kg).
  4. Mélanges à base de masses de moulage thermoplastiques suivant l'une des revendications 1 à 3, comprenant jusqu'à 45% en poids de masses de moulage thermoplastiques qui présentent la même structure chimique, l'indice de viscosité du polymère A ainsi que la grosseur des particules de caoutchouc B pouvant cependant être quelconques.
  5. Demi-produits façonnés, en particulier profilés, feuilles ou plaques, préparés par coextrusion de 0,1 à 50% en poids, de préférence de 2 à 20% en poids, de masses de moulage suivant l'une des revendications 1 à 3, et de 50 à 99,9% en poids, de préférence de 80 à 98% en poids, d'une deuxième masse de moulage thermoplastique, formée à partir d'un des polymères suivants : ABS, PVC, HIPS, SAN, ASA + PC ou ABS + PC.
  6. Demi-produits façonnés suivant la revendication 5, caractérisés par un rapport entre l'indice de fusion (selon ISO 1133 à 220°C et 10 kg) de la première masse de moulage et celui de la deuxième masse de moulage de 0,5 à 10, de préférence de 1 à 10.
  7. Demi-produits suivant l'une des revendications 5 et 6, caractérisés en ce que la teneur en acrylonitrile de la première masse de moulage est plus grande que la teneur en acrylonitrile de la deuxième masse de moulage.
  8. Demi-produits de façonnage suivant l'une des revendications 5 à 7, caractérisés en ce que les particules du caoutchouc B présentent une morphologie de réseau.
  9. Procédé de préparation de demi-produits de façonnage suivant l'une des revendications 5 à 8, par coextrusion.
  10. Procédé suivant la revendication 9, caractérisé en ce que les pièces façonnées coextrudées sont embouties.
  11. Procédé suivant l'une des revendications 9 et 10, caractérisé en ce que la température de traitement de la première masse de moulage est de 200 à 300°C, de préférence de 210 à 280°C.
EP99944455A 1998-08-20 1999-08-20 Matiere moulable asa pour la production de pieces de moulage mates Revoked EP1109860B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19837854A DE19837854A1 (de) 1998-08-20 1998-08-20 Thermoplastische Formmassen
DE19837854 1998-08-20
PCT/EP1999/006114 WO2000011080A1 (fr) 1998-08-20 1999-08-20 Matiere moulable asa pour la production de pieces de moulage mates

Publications (2)

Publication Number Publication Date
EP1109860A1 EP1109860A1 (fr) 2001-06-27
EP1109860B1 true EP1109860B1 (fr) 2003-01-02

Family

ID=7878184

Family Applications (1)

Application Number Title Priority Date Filing Date
EP99944455A Revoked EP1109860B1 (fr) 1998-08-20 1999-08-20 Matiere moulable asa pour la production de pieces de moulage mates

Country Status (6)

Country Link
US (1) US6683133B1 (fr)
EP (1) EP1109860B1 (fr)
AT (1) ATE230425T1 (fr)
DE (2) DE19837854A1 (fr)
ES (1) ES2190247T3 (fr)
WO (1) WO2000011080A1 (fr)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100450230B1 (ko) * 2001-12-04 2004-09-24 주식회사 엘지화학 접착력이 우수한 열가소성 수지 조성물
US7550536B2 (en) * 2001-12-25 2009-06-23 Jsr Corporation Acrylic rubber, process for its production, and rubber compositions, oil-and weather-resistant rubber compositions, and oil-and weather -resistant rubbers, containing the same
US8969476B2 (en) * 2002-06-21 2015-03-03 Sabic Global Technologies B.V. Impact-modified compositions
DE10228376A1 (de) * 2002-06-25 2004-01-15 Basf Ag Formteil umfassend eine Verbundschichtplatte oder -folie und eine Trägerschicht
KR20110031218A (ko) * 2008-07-07 2011-03-24 바스프 에스이 고무-개질된 난연성 성형 조성물
US20140323606A1 (en) 2010-12-16 2014-10-30 Basf Se Rubber-modified flame-retardant moulding compositions and production thereof
JP6834970B2 (ja) 2015-10-28 2021-02-24 テクノＵｍｇ株式会社 グラフト共重合体の製造方法、およびそれを用いた熱可塑性樹脂組成物の製造方法
CN112831170A (zh) * 2021-01-05 2021-05-25 上海中镭新材料科技有限公司 一种免喷涂哑光pc/asa合金树脂及其制备方法

Family Cites Families (8)

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Publication number Priority date Publication date Assignee Title
DE3615608A1 (de) 1986-05-09 1987-11-12 Basf Ag Thermoplastische formmasse auf basis von polycarbonat, 2 pfropfmischpolymerisaten unterschiedlicher pfropfgrundlage (asa + aes) und vinylaromat/an enthaltenden copolymerisaten
DE3615607A1 (de) * 1986-05-09 1987-11-12 Basf Ag Thermoplastische formmasse auf basis von polycarbonat, asa und vinylaromaten/an enthaltenden copolymerisaten
CA1337104C (fr) 1986-11-18 1995-09-26 William James Work Polymeres thermoplastiques dispersant la lumiere
DE4221293A1 (de) 1992-06-29 1994-01-05 Basf Ag Formmasse mit matter Oberfläche
DE4446896A1 (de) * 1994-12-27 1996-07-04 Basf Ag Schlagzähne, thermoplastisch verarbeitbare Mischung aus Elastomeren und Thermoplasten
IL119719A0 (en) 1996-11-29 1997-02-18 Yeda Res & Dev Inorganic fullerene-like structures of metal chalcogenides
DE19702733A1 (de) * 1997-01-27 1998-07-30 Basf Ag Thermoplastische Formmassen mit hoher Zähigkeit
US5883191A (en) 1997-09-24 1999-03-16 Hughes Processing, Inc. Acrylonitrile/styrene/acrylic polymeric materials and methods for making same

Also Published As

Publication number Publication date
US6683133B1 (en) 2004-01-27
DE59903922D1 (de) 2003-02-06
ATE230425T1 (de) 2003-01-15
ES2190247T3 (es) 2003-07-16
DE19837854A1 (de) 2000-02-24
EP1109860A1 (fr) 2001-06-27
WO2000011080A1 (fr) 2000-03-02

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